CN111180705B - Lithium-sulfur battery electrode material with ultralow self-discharge and preparation method thereof - Google Patents
Lithium-sulfur battery electrode material with ultralow self-discharge and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lithium-sulfur battery electrode material with ultralow self-discharge and a preparation method thereof. The lithium-sulfur electrode material provided by the invention is a composite material formed by cobalt/nitrogen-doped hollow polyhedron/carbon nano tube/sulfur simple substance derived from a bimetallic organic framework. The electrode material solves the problems of common volume expansion, poor conductivity and the like of the lithium-sulfur battery. More importantly, the shuttle effect in the lithium-sulfur battery is overcome by means of strong chemical adsorption and catalytic polysulfide rapid conversion of cobalt particles and nitrogen heteroatoms, so that the cycle stability of the lithium-sulfur battery is improved (the cycle loss rate of each circle is 0.12%), and the self-discharge phenomenon of the lithium-sulfur battery is greatly limited. After standing for 68 days, the specific capacity loss rate per day is only 0.18%, and the self-discharge still has stable cycle performance.
Description
Technical Field
The invention belongs to the technical field of electrochemical cells, and particularly relates to a lithium-sulfur cell electrode material with ultralow self-discharge and a preparation method thereof.
Background
The lithium-sulfur battery has high theoretical specific capacity (1675mAh g)-1) High theoretical energy density (2600Wh kg)-1) And the advantages of rich elemental sulfur content, low cost, environmental friendliness and the like, the lithium-sulfur battery is considered to be one of the best choices for the next-generation secondary battery system. However,volume change during charging and discharging of Lithium-Sulfur Batteries, insulation of elemental Sulfur and Discharge products and hysteresis conversion kinetics thereof, and soluble polysulfide shuttling behavior lead to poor cycling stability, high Self-Discharge, and a loss of 50% of specific capacity upon standing for one month (Chung S-H, and manthiam A Lithium-Sulfur Batteries with the Lowest Self-Discharge and the Longest Shelf life [ J]ACS Energy Letters,2017,2(5): 1056-.
In order to solve the problems, a carbon material is added into a sulfur positive electrode to construct a composite positive electrode, so that the conductivity can be improved, and the shuttle effect can be relieved. Polar metal compounds can limit the shuttling behavior of polysulfides by chemisorption, but their low conductivity is not conducive to rapid polysulfide switching, and eventually the accumulated polysulfide can still diffuse. Recently, special transition metals and their compounds having catalytic and adsorptive activities have been greatly limited in shuttle effect by virtue of strong chemisorption and accelerated polysulfide conversion reaction. However, most of the transition metal and compound particles thereof are extremely easy to agglomerate, so that the catalytic and adsorption activity is limited, and the shuttle effect still occurs. The direct exposure of the metal and the compound thereof in the electrolyte can also bring about some side reactions, and the structure of the particle of the metal and the compound thereof cannot improve the sulfur content and the sulfur carrying capacity, and cannot meet the requirement of high energy density of the lithium-sulfur battery.
Disclosure of Invention
In view of the problems of the prior art, the present invention provides an electrode material for a lithium-sulfur battery having ultra-low self-discharge and a method for preparing the same. The invention uses metal salt and organic ligand as raw materials to prepare metal organic framework, and obtains the cobalt/nitrogen doped hollow polyhedron/carbon nano tube/sulfur composite material electrode material through the processes of high-temperature carbonization and melting composite sulfur simple substance. The material is applied to the positive electrode material of the lithium-sulfur battery and has good cycle stability and ultralow self-discharge performance.
The invention claims a method for preparing a cobalt-nitrogen doped hollow polyhedron/carbon nanotube material, which comprises the following steps:
1) respectively dissolving an organic ligand and a metal salt in a solvent to obtain a solution a and a solution b in sequence;
pouring the solution a into the solution b, mixing uniformly, washing, centrifuging and drying, and dissolving the dried product into the solvent again to obtain a solution c;
uniformly mixing the metal salt and the organic ligand in the solvent with the solution c to obtain a solution d, centrifuging, washing and drying to obtain a core-shell bimetallic organic framework compound;
2) carbonizing the core-shell bimetallic organic framework compound obtained in the step 1) under the protection of inert atmosphere to obtain the core-shell bimetallic organic framework compound.
In step 1) of the above method, the organic ligand is at least one selected from the group consisting of 2-methylimidazole, 1-methylimidazole and 2-ethyl-4-methylimidazole;
the metal salt is selected from at least one of zinc nitrate, zinc acetate and zinc sulfate;
the solvent in the metal salt solution is the solvent;
the solvent is at least one selected from ethylene glycol, methanol and water;
in the solution a, the molar concentration of the organic ligand is 0.1-1 mol/L; specifically 0.43-0.5 mol/L;
in the solution b, the molar concentration of the metal salt is 0.1-0.5 mol/L; specifically 0.25 mol/L;
in the solution d, the molar concentration of the metal salt is 0.03-1 mol/L; specifically 0.09-0.14 mol/L; the molar concentration of the organic ligand is 0.2-2 mol/L; in particular 0.44-0.5 mol/L.
In the washing step, the washing agent is methanol and water; the number of times of centrifugal washing is three; the drying step may be carried out under specific conditions of 60 ℃ for 12 hours.
In the step 2) of carbonization, the temperature rising rate from room temperature to the carbonization temperature is 1-10 ℃ for min-1(ii) a In particular at 2 ℃ min-1；
The carbonization temperature is 700-1000 ℃; specifically 900 ℃;
the carbonization time is 1-5 h; in particular 2-3 h;
the cooling rate from the carbonization temperature to the room temperature is 1-10 ℃ min-1(ii) a Specifically 5 deg.C min-1；
The inert atmosphere is argon atmosphere.
In addition, the cobalt-nitrogen doped hollow polyhedron/carbon nanotube material prepared by the method also belongs to the protection scope of the invention.
The present invention also claims a method of preparing an electrode material for a lithium sulfur battery, the method comprising:
and uniformly mixing the cobalt-nitrogen doped hollow polyhedron/carbon nanotube material with sulfur powder, and melting to obtain the cobalt-nitrogen doped hollow polyhedron/carbon nanotube material.
In the melting step of the method, the mass ratio of the cobalt-nitrogen doped hollow polyhedron/carbon nanotube material to the sulfur powder is 1: 2-9; specifically 3: 7;
the temperature rising rate from room temperature to the melting temperature is 0.5-2 ℃ for min-1(ii) a Specifically 1 deg.C min-1；
The melting temperature is 150-200 ℃; in particular 160-180 ℃;
the melting time is 12-24 h.
In addition, the lithium-sulfur battery electrode material prepared by the method, the battery containing the lithium-sulfur battery electrode material and the application of the lithium-sulfur battery electrode material as a battery cathode material in self-discharge also belong to the protection scope of the invention.
The beneficial effects of the invention include:
the invention designs a cobalt/nitrogen doped hollow polyhedron/carbon nanotube material derived from a metal organic framework, and further compounds a sulfur simple substance as a lithium sulfur positive electrode material. The hollow polyhedron can not only contain enough elemental sulfur, but also inhibit the volume expansion in the charging and discharging process; secondly, the carbon nano tube can improve the conductivity of the electrode material; the cobalt particles with catalytic and adsorption properties, which are embedded in the carrier, adsorb polysulfide chemically and accelerate polysulfide conversion, and finally solve the problem of shuttle effect.
The material prepared by the invention solves the problems of common volume expansion, poor conductivity and the like of the lithium-sulfur battery. More importantly, the shuttle effect in the lithium-sulfur battery is overcome by means of strong chemical adsorption and catalytic polysulfide rapid conversion of cobalt particles and nitrogen heteroatoms, so that the cycle stability of the lithium-sulfur battery is improved (the cycle loss rate of each circle is 0.12%), and the self-discharge phenomenon of the lithium-sulfur battery is greatly limited. The material is applied to a lithium-sulfur battery, after 290 circles of circulation under the current density of 0.2C, the capacity loss rate of each circle is 0.071%, after 68 days of standing, the capacity loss rate of each day is only 0.1%, the circulation is continued for 65 circles, and the capacity retention rate is 111%.
Drawings
Fig. 1 is an X-ray diffraction pattern of the cobalt/nitrogen-doped hollow polyhedron/carbon nanotube material prepared in example 1.
Fig. 2 is a scanning electron microscope image of the cobalt/nitrogen-doped hollow polyhedron/carbon nanotube prepared in example 1.
Fig. 3 is a transmission electron microscope image of the cobalt/nitrogen-doped hollow polyhedron/carbon nanotube prepared in example 1.
Fig. 4 is a graph of the cycle performance before and after self-discharge of the assembled lithium sulfur battery of example 1.
Fig. 5 is a graph of the cycle performance before and after self-discharge of the assembled lithium sulfur battery of example 2.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Examples 1,
1) 4.46g of zinc nitrate (molar concentration of 0.1mol/L) and 5.4g of 2-methylimidazole (molar concentration of 0.43mol/L) were dissolved in 150mL of methanol, respectively, and then the solution containing dimethylimidazole (i.e., solution a) was poured into the zinc nitrate solution (i.e., solution b) and stirred magnetically for 24 hours. After centrifugal washing is carried out for three times by using methanol and water, drying is carried out for 12h at the temperature of 60 ℃ to obtain a dried product;
the obtained dry product, namely white powder, is dissolved in 100mL of methanol, then 3.9g of cobalt nitrate (with a molar concentration of 0.09mol/L) and 5.4g of dimethylimidazole (with a molar concentration of 0.44mol/L) are respectively dissolved in 150mL of methanol solution, and the solution is sequentially added into the above solution and stirred for 24 hours to be mixed uniformly, so as to obtain a solution d. Centrifugally washing the core-shell bimetallic organic framework compound for three times by using methanol and water, and drying the core-shell bimetallic organic framework compound to obtain a core-shell bimetallic organic framework compound;
2) under the protection of inert atmosphere, carbonizing the core-shell bimetallic organic framework compound obtained in the step 1) at 900 ℃ for 2h, and raising the temperature for 2 min-1. The cooling rate is 5 deg.C for min-1To obtain a cobalt-nitrogen doped hollow polyhedron/carbon nanotube material;
3) uniformly mixing the cobalt-nitrogen doped hollow polyhedron/carbon nanotube material and elemental sulfur according to the mass ratio of 3:7, adding the mixture into a sealed tank filled with argon, heating the mixture for 24 hours at 160 ℃ in a muffle furnace, and heating the mixture at the rate of 1 ℃ for min-1And obtaining the cobalt/nitrogen doped hollow polyhedron/carbon nano tube/sulfur composite material.
Mixing the composite material with polyvinylidene fluoride and acetylene black according to the weight ratio of 8: 1:1 proportion, evenly mixing the mixture in N-methyl pyrrolidone, coating the mixture on carbon paper by a scraper, drying the carbon paper, and cutting the carbon paper into electrode slices with the diameter of 11mm (the sulfur carrying capacity of a single slice is 2.3mg cm)-2) The lithium sheet is used as a negative electrode, the celgard 2325 is used as a diaphragm, a 1mol/L lithium bis (trifluoromethylsulfonyl) imide solution is used as an electrolyte solution, a solvent is a mixed solution of 1, 3-dioxolane and ethylene glycol dimethyl ether (the volume ratio v/v is 1:1), 0.2mol/L lithium nitrate is used as an electrolyte, and the mass ratio of the electrolyte to sulfur is 15 mu L mg-1And after standing for 24 hours, testing the cycle performance before and after self-discharge at the voltage of 1.8-2.8V and at 0.2C.
Fig. 1 is an X-ray diffraction pattern of the cobalt/nitrogen-doped hollow polyhedron/carbon nanotube/sulfur composite material prepared in this example, which proves that the composite material was successfully synthesized.
Fig. 2 is a scanning electron microscope image of the cobalt/nitrogen-doped hollow polyhedron/carbon nanotube material prepared in this embodiment, through which the structure having a regular polyhedron and a large number of carbon nanotubes can be clearly observed.
Fig. 3 is a transmission electron microscope image of the cobalt/nitrogen-doped hollow polyhedron/carbon nanotube material prepared in this example, in which the hollow polyhedron and the embedded cobalt particles can be visually observed.
Fig. 4 shows the cycle performance of the cobalt/nitrogen-doped hollow polyhedron/carbon nanotube/sulfur positive electrode material prepared in this embodiment before and after self-discharge, after 290 cycles of circulation at a current density of 0.2C, the capacity loss rate of each cycle is 0.071%, after 68 days of standing, the capacity loss rate of each day is only 0.1%, and after 65 cycles of continuous circulation, the capacity retention rate is 111%.
Example 2:
1) 7.3g of zinc nitrate (molar concentration of 0.25mol/L) and 6.12g of 2-methylimidazole (molar concentration of 0.5mol/L) were dissolved in 150mL of water, respectively, and then the solution containing dimethylimidazole (i.e., solution a) was poured into the zinc nitrate solution (i.e., solution b) and stirred magnetically for 24 hours. After centrifugal washing is carried out for three times by using methanol and water, drying is carried out for 12h at the temperature of 60 ℃ to obtain a dried product;
the obtained dry product, namely white powder, is dissolved in 100mL of water, then 6.2g (molar concentration is 0.14mol/L) of cobalt nitrate and 6.12g of dimethylimidazole (molar concentration is 0.5mol/L) are respectively dissolved in 150mL of water, and the mixture is sequentially added into the solution and stirred for 24 hours to be mixed uniformly, so as to obtain a solution d. Centrifugally washing the core-shell bimetallic organic framework compound for three times by using methanol and water, and drying the core-shell bimetallic organic framework compound to obtain a core-shell bimetallic organic framework compound;
2) under the protection of inert atmosphere, carbonizing the core-shell bimetallic organic framework compound obtained in the step 1) at 700 ℃ for 3h, and raising the temperature for 2 ℃ for min-1The cooling rate is 5 ℃ for min-1To obtain a cobalt-nitrogen doped hollow polyhedron/carbon nanotube material;
3) uniformly mixing the cobalt-nitrogen doped hollow polyhedron/carbon nanotube material and elemental sulfur according to the mass ratio of 3:7, adding the mixture into a sealed tank filled with argon, heating the mixture for 12 hours at 180 ℃ in a muffle furnace, and heating the mixture at the rate of 0.5 ℃ for min-1And obtaining the cobalt/nitrogen doped hollow polyhedron/carbon nano tube/sulfur composite material.
Mixing the composite material with polyvinylidene fluoride and acetylene black according to the weight ratio of 8: 1:1 proportion, evenly mixing the mixture in N-methyl pyrrolidone, coating the mixture on carbon paper by a scraper, drying the carbon paper, and cutting the carbon paper into electrode slices with the diameter of 11mm (the sulfur carrying amount of a single slice is 3.7mg cm)-2) The lithium sheet is used as a negative electrode, the celgard 2325 is used as a diaphragm, a 1mol/L lithium bis (trifluoromethylsulfonyl) imide solution is used as an electrolyte solution, and the solvent is 1, 3-dioxolane anda mixed solution of ethylene glycol dimethyl ether (volume ratio v/v ═ 1:1) and 0.2mol/L lithium nitrate as an electrolyte, and the mass ratio of the electrolyte to sulfur was 30. mu.L mg-1And after standing for 24 hours, testing the cycle performance before and after self-discharge at the voltage of 1.8-2.8V and at 0.2C.
The X-ray diffraction pattern, the scanning electron microscope image and the transmission electron microscope image of the cobalt/nitrogen-doped hollow polyhedron/carbon nano tube/sulfur composite material prepared in the embodiment are not substantially different from those of the embodiment 1.
Fig. 5 shows the cycle performance of the cobalt/nitrogen-doped hollow polyhedron/carbon nanotube/sulfur positive electrode material prepared in this example before and after self-discharge, after 300 cycles at a current density of 0.2C, the capacity loss rate per cycle is 0.13%, after standing for 68 days, the capacity loss rate per day is only 0.18%, and after 70 cycles, the capacity retention rate is 106%.
Claims (7)
1. A method of making a lithium sulfur battery electrode material, comprising:
uniformly mixing a cobalt-nitrogen doped hollow polyhedron/carbon nanotube material and sulfur powder, and melting to obtain the cobalt-nitrogen doped hollow polyhedron/carbon nanotube material;
the method for preparing the cobalt-nitrogen doped hollow polyhedron/carbon nanotube material comprises the following steps:
1) respectively dissolving an organic ligand and a metal salt in a solvent to obtain a solution a and a solution b in sequence; the metal salt is selected from at least one of zinc nitrate, zinc acetate and zinc sulfate;
pouring the solution a into the solution b, mixing uniformly, washing, centrifuging and drying, and dissolving the dried product into the solvent again to obtain a solution c;
uniformly mixing metal salt cobalt nitrate and an organic ligand in the solvent with the solution c to obtain a solution d, centrifuging, washing and drying to obtain a core-shell bimetallic organic framework compound;
2) carbonizing the core-shell bimetallic organic framework compound obtained in the step 1) under the protection of inert atmosphere to obtain the core-shell bimetallic organic framework compound.
2. The method of claim 1, wherein: in the step 1), the organic ligand is selected from at least one of 2-methylimidazole, 1-methylimidazole and 2-ethyl-4-methylimidazole;
the solvent in the metal salt solution is the solvent;
the solvent is at least one selected from ethylene glycol, methanol and water;
in the solution a, the molar concentration of the organic ligand is 0.1-1 mol/L;
in the solution b, the molar concentration of the metal salt is 0.1-0.5 mol/L;
in the solution d, the molar concentration of the metal salt is 0.03-1 mol/L; the molar concentration of the organic ligand is 0.2-2 mol/L.
3. The method of claim 1, wherein: in the step 2) of carbonization, the temperature rising rate from room temperature to the carbonization temperature is 1-10 ℃ for min-1；
The carbonization temperature is 700 ℃ and 1000 ℃;
the carbonization time is 1-5 h;
the cooling rate from the carbonization temperature to the room temperature is 1-10 ℃ min-1；
The inert atmosphere is argon atmosphere.
4. A method according to any one of claims 1 to 3, wherein: in the melting step, the mass ratio of the cobalt-nitrogen doped hollow polyhedron/carbon nanotube material to the sulfur powder is 1: 2-9;
the temperature rising rate from room temperature to the melting temperature is 0.5-2 ℃ for min-1；
The melting temperature is 150 ℃ and 200 ℃;
the melting time is 12-24 h.
5. A lithium-sulfur battery electrode material prepared by the method of any one of claims 1 to 4.
6. A battery comprising the lithium sulfur battery electrode material according to claim 5.
7. Use of the lithium sulfur battery electrode material according to claim 6 as a battery positive electrode material in self-discharge.
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